JPH0211589B2 - - Google Patents
Info
- Publication number
- JPH0211589B2 JPH0211589B2 JP54124571A JP12457179A JPH0211589B2 JP H0211589 B2 JPH0211589 B2 JP H0211589B2 JP 54124571 A JP54124571 A JP 54124571A JP 12457179 A JP12457179 A JP 12457179A JP H0211589 B2 JPH0211589 B2 JP H0211589B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- isomer
- alkyl group
- formula
- nmr spectrum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- -1 triazole compounds Chemical class 0.000 claims description 19
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- 150000001336 alkenes Chemical group 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 6
- 125000004647 alkyl sulfenyl group Chemical group 0.000 claims description 5
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 5
- 125000001188 haloalkyl group Chemical group 0.000 claims description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 8
- JLIDVCMBCGBIEY-UHFFFAOYSA-N 1-penten-3-one Chemical compound CCC(=O)C=C JLIDVCMBCGBIEY-UHFFFAOYSA-N 0.000 description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 241000209219 Hordeum Species 0.000 description 6
- 235000007340 Hordeum vulgare Nutrition 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 241000221785 Erysiphales Species 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 150000003852 triazoles Chemical group 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003905 agrochemical Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 201000010099 disease Diseases 0.000 description 3
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 230000000855 fungicidal effect Effects 0.000 description 3
- 239000000417 fungicide Substances 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 125000001425 triazolyl group Chemical group 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- RGGXVDKXZOPPIV-UHFFFAOYSA-N 4,4-dimethyl-2-(1,2,4-triazol-1-yl)pent-1-en-3-one Chemical compound CC(C)(C)C(=O)C(=C)N1C=NC=N1 RGGXVDKXZOPPIV-UHFFFAOYSA-N 0.000 description 1
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241000221787 Erysiphe Species 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 238000003898 horticulture Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000007699 photoisomerization reaction Methods 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 244000000003 plant pathogen Species 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
本発明は一般式〔〕
〔式中、Xは同一または相異なり、アルキル基、
ハロアルキル基、アルコキシ基、フエノキシ基、
シアノ基またはニトロ基を表わし、nは0〜5の
整数を表わし、Rはアルキル基、シクロプロピル
基、またはアルキルスルフエニル基で置換された
アルキル基を表わす。
但し、Rがターシヤリブチル基を表わし、かつ
Xがハロゲン原子またはフエニル基を表わし、n
が1または2を表わす場合を除く。〕
で示されるトリアゾール系化合物の2つの幾何異
性体のうち、オレフインプロトンが重クロロホル
ム中でのNMRスペクトル上、より高磁場側に現
われる幾何異性体化合物およびその製造法に関す
るものである。
本発明化合物〔〕のX、nおよびRの好適な
例をあげるならば、Xはメチル基、エチル基、プ
ロピル基、イソプロピル基、ブチル基、t−ブチ
ル基などの直鎖もしくは分枝したアルキル基、メ
トキシ基、エトキシ基、プロポキシ基、イソプロ
ポキシ基、ブトキシ基などの直鎖もしくは分枝し
たアルコキシ基、トリフロロメチル基に代表され
るハロ置換アルキル基、フエノキシ基、フエニル
基、シアノ基またはニトロ基であり、nは0.1ま
たは2が特に好ましく、Rはメチル基、エチル
基、プロピル基、ブチル基などの直鎖のアルキル
基、イソプロピル基、t−ブチル基、sec−ブチ
ル基などの分枝したアルキル基、シクロプロピル
基またはアルキルスルフエニル基で置換されたア
ルキル基(たとえば2−メチルスルフエニルプロ
パン−2−イル基)などが好ましい。
従来、農園芸作物の病害虫に対して活性を有
し、農薬として農園芸用作物の安定供給に多大の
寄与をなした数多くの合成有機化合物が開発され
ているが、より改良されるべき問題が数多く存在
することも事実である。そのような問題は、たと
えば、新しいより有効な薬剤の開発によつて解決
される場合もあるし、また従来の薬剤を検討して
より有効な農業体系を確立することによつても解
決されていくことも考えられる。
合成有機化合物の多くは化学構造上幾何異性体
や光学異性体など異性体の存在の可能性を有する
ものが少なくないし、実際に農薬として使用され
ている薬剤のうちでもこれらの異性体を含んだま
ま用いられている例も多い。異性体を有する生理
活性物質の多くはそれら異性体間で生理活性に差
が認められることは農薬に限らず多くの例で知ら
れている。近年、農園芸分野において環境汚染の
問題が多々論ぜられているが、このような異性体
混合物のうちより有効な活性を有する一方の異性
体を使用することによつて環境汚染の軽減をはか
ることは重要である。またこのことは化合物の製
造工程においても、農薬としての実際の使用場合
においてもより経済的な効果をもたらすものと考
えられる。かかる見地からより有効な活性を有す
る異性体を提供すること、またはその中間体を工
業的に実施可能な方法で提供することはこの分野
において充分貢献することと考えられる。
本発明者らは下記一般式〔〕
〔式中、R1は
The present invention is based on the general formula [] [In the formula, X is the same or different, an alkyl group,
haloalkyl group, alkoxy group, phenoxy group,
It represents a cyano group or a nitro group, n represents an integer of 0 to 5, and R represents an alkyl group, a cyclopropyl group, or an alkyl group substituted with an alkylsulfenyl group. However, R represents a tertiary butyl group, X represents a halogen atom or a phenyl group, and n
except when represents 1 or 2. ] Among the two geometric isomers of triazole compounds shown in the following, the olefin proton appears on the higher magnetic field side in the NMR spectrum in deuterated chloroform, and the method for producing the same. To give preferable examples of X, n and R in the compound of the present invention [], straight-chain or branched alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, and butoxy groups, halo-substituted alkyl groups such as trifluoromethyl, phenoxy, phenyl, cyano, or It is a nitro group, and n is particularly preferably 0.1 or 2. Preferred are branched alkyl groups, cyclopropyl groups, or alkyl groups substituted with alkylsulfenyl groups (for example, 2-methylsulfenylpropan-2-yl groups). To date, many synthetic organic compounds have been developed that have activity against pests of agricultural and horticultural crops and have greatly contributed to the stable supply of agricultural and horticultural crops as pesticides, but there are still issues that need to be improved. It is also true that there are many. Such problems may be solved, for example, by developing new, more effective drugs, or by reviewing traditional drugs to establish more effective agricultural systems. I can also think of going. Many synthetic organic compounds have the possibility of the existence of isomers such as geometric and optical isomers due to their chemical structures, and even the drugs actually used as agricultural chemicals contain these isomers. There are many examples where it is still used. It is known that many physiologically active substances having isomers exhibit differences in physiological activity between the isomers, not only in agricultural chemicals but also in many other cases. In recent years, the issue of environmental pollution has been much discussed in the field of agriculture and horticulture, but it is possible to reduce environmental pollution by using one of these isomer mixtures that has more effective activity. That is important. Moreover, this is thought to bring about more economical effects both in the manufacturing process of the compound and in the actual use as an agricultural chemical. From this point of view, it is considered that providing an isomer with more effective activity or providing an intermediate therefor by an industrially feasible method will make a sufficient contribution to this field. The present inventors have the following general formula [] [In the formula, R 1 is
【式】または[expression] or
【式】で示
されるイミダゾリル基またはトリアゾリル基を表
わす。R2は炭素数1〜4の直鎖もしくは分岐し
たアルキル基を表わす。Yは炭素数1〜4の直鎖
もしくは分岐したアルキル基、ハロゲン原子、ニ
トロ基、シアノ基、アセトキシ基、トリフロロメ
チル基、ジメチルアミノ基、OR′で表わされるア
ルコキシ基またはフエノキシ基を表わす。R′は
炭素数1〜4のアルキル基または無置換もしくは
ハロゲン原子で置換されたフエニル基を表わす。
nは0〜3の整数を表わす。〕
で示されるアゾール系化合物(特開昭53−130661
号公報)および下記一般式〔〕
〔式中、Zはアルキル基、シアノ基、アルコキシ
基、フエノキシ基、ハロゲン原子または水素原子
を表わし、mは1〜5の整数を表わす。R1は
Represents an imidazolyl group or triazolyl group represented by the formula. R 2 represents a straight chain or branched alkyl group having 1 to 4 carbon atoms. Y represents a straight-chain or branched alkyl group having 1 to 4 carbon atoms, a halogen atom, a nitro group, a cyano group, an acetoxy group, a trifluoromethyl group, a dimethylamino group, an alkoxy group represented by OR', or a phenoxy group. R' represents an alkyl group having 1 to 4 carbon atoms or a phenyl group that is unsubstituted or substituted with a halogen atom.
n represents an integer from 0 to 3. ] The azole compound represented by (JP-A-53-130661
Publication) and the following general formula [] [In the formula, Z represents an alkyl group, a cyano group, an alkoxy group, a phenoxy group, a halogen atom or a hydrogen atom, and m represents an integer of 1 to 5. R 1 is
【式】で示されるイミダゾリル基またはAn imidazolyl group represented by [Formula] or
【式】で示されるトリアゾリル基を表わ
す。R2はtert−ブチル基または無置換あるいは随
意にアルキル基、アルコキシ基、フエニル基もし
くはハロゲン原子で置換されたフエニル基を表わ
す。〕
で示されるアゾール系化合物(特開昭54−41875
号公報)が殺菌剤として優れた性質を有すること
を見出した。
一般式〔〕で示されるトリアゾール系化合物
は、前記記載の公報(特開昭53−130661号公報)
に示される如く、たとえば下記反応に従つて製造
できるが、
〔式中、X、nおよびRは先に述べた意味と同一
である。〕
通常は下記一般式〔〕および〔〕で示され
る幾何異性体の混合物として得られる。
〔式中、X、nおよびRは先に述べた意味と同一
である。〕
本発明者らは前記のような立場からさらに研究
を続けた結果
(1) 一般式〔〕および〔〕の幾何異性体ケト
ン化合物の各々を還元して得られるアルコール
化合物の幾何異性体の一方が他方に比べてより
広範な植物病原菌に対して非常に高い殺菌活性
を有するなど農園芸殺菌剤としての優れた性質
を有する。
(2) 一般式〔〕で示されるトリアゾール系化合
物の幾何異性体の一方または幾何異性体の混合
物を光照射することにより、事実上定量的に、
より活性の高いアルコール化合物を製造するた
めの中間体となるケトン化合物の幾何異性体を
製造しうる
ことを見出し、本発明の完成に至つたものであ
る。すなわち、一般式〔〕で示されるトリアゾ
ール系化合物の2つの幾何異性体は、たとえばそ
の融点の違い、ガスクロマトグラフイーまたは
NMRスペクトルによつて特徴付けることがで
き、たとえば、一般式〔〕で示されるトリアゾ
ール系化合物の幾何異性体の一方(以下〔〕−
−E異性体と称する)のオレフインプロトンは、
重クロロホルム中でのNMRスペクトル上、他方
の幾何異性体(以下〔〕−z異性体と称する)
のオレフインプロトンよりも高磁場側に現われる
が、〔〕−E異性体を還元して得られるアルコー
ル化合物(以下アルコール−E異性体と称する)
は〔〕−Z異性体を還元して得られるアルコー
ル化合物(以下アルコール−Z異性体と称する)
に比してより広範な病原菌に対して、より高い殺
菌活性を示し〔〕−E異性体は、より優れた性
質を有する農園芸用殺菌剤を製造するための重要
な中間体と言える。〔〕−E異性体は前記反応式
に従つて得られる異性体混合物から分別結晶化に
よる方法やカラムクロマトグラフイーによつて純
粋に得ることもできるが(参考例1参照)、本発
明の方法によつてより効率よく製造することがで
きる。すなわち、〔〕−Z異性体を光の照射下に
置くことにより事実上定量的に〔〕−E異性体
に変換することができた。〔〕−Zおよび〔〕
−E異性体の任意の混合物を同様の条件下におい
ても同じく事実上定量的に〔〕−E異性体に変
換されることが判明し、本発明は〔〕−E異性
体を製造するための優れた方法を提供するもので
あると言える。以下、本発明化合物を製造するよ
り具体的な方法を述べる。
〔〕−Z異性体または〔〕−Zおよび〔〕
−E異性体の混合物を通常は光に対して不活性な
溶媒中、UVランプやキセノンランプなどの光照
射下に置くことによつて、また実験室的には螢光
灯や太陽光線下に置くことによつて〔〕−E異
性体を製造することができる。通常使用される溶
媒は、たとえばメタノール、エタノール、プロパ
ノールなどのアルコール類、エーテル、テトラヒ
ドロフラン、ジオキサンなどのエーテル類、アセ
トン、メチルエチルケトン、メチルイソブチルケ
トンなどのケトン類、ヘキサン、シクロヘキサ
ン、石油エーテルなどの脂肪族炭化水素類、ベン
ゼン、トルエン、キシレンなどの芳香族炭化水素
類などがあげられる。反応の温度は通常の光異性
化反応を行なう温度で行ないうるが、実際の製造
上では0℃〜100℃の範囲で行なわれるのが好ま
しい。また通常の光反応に使用される増感剤、た
とえばアセトフエノン、プロピオフエノンなどの
フエニルケトン類を添加して反応を行なうこと
も、もちろん可能であるが、特に大きな利点は見
出されない。
なお本発明化合物は、それ自体各種の農業上有
害な病原菌に対して強い殺菌力を有し、有用な殺
菌剤として使用可能なものである(参考例2参
照)とともに除草および植物生長調節作用も有
し、この分野での使用の可能性も認められる。
次に実施例および参考例をあげて本発明をさら
に詳細に説明する。
参考例 1
1−(4−メチルフエニル)−4,4−ジメチル
−2−(1,2,4−トリアゾール−1−イル)
−1−ペンテン−3−オンの合成(幾何異性体
混合物)
α−(1,2,4−トリアゾール−1−イル)
ピナコロン50g、無水炭酸カリウム41g、無水酢
酸200ml、4−クロロベンズアルデヒド39.7gを
混合し、撹拌下90℃にて12時間加熱した。反応液
を冷却後、沈澱物を過して除いた。母液を60℃
の温水500mlに滴下して無水酢酸を分解し、つい
で炭酸カリウムを少量ずつ加えてアルカリ性とな
し、生成し油状物を酢酸エチル500mlで抽出した。
有機層を無水硫酸ナトリウムで乾燥後、減圧下に
濃縮した。残渣の一滴をとつてアセトン溶液とな
し下記条件下でのガスクロマトグラフイーを行な
つたところリテンシヨンタイム250secに〔〕−
E異性体に相当するピークを、300secに〔〕−
Z異性体に相当するピークを認めた。その面積百
分率から求められる存在比は1/4であつた。
ガスクロマトグラフイーの条件は以下のとおり
である。
装置:日本電子20KFID検出器
カラム :5%XE−60、担体クロモソルブW、
1mガラスカラム
カラム温度:200℃
気化室温度:240℃
キヤリヤーガス:窒素ガス1Kg/cm2
残渣を100mlのベンゼンに溶解し、1.2Kgのシリ
カゲル(100〜200メツシユ)を含むカラムに通し
た後、n−ヘキサン/アセトン(10/1)を展開
溶媒としてカラムクロマトグラフイーを行なつ
た。各々得られた異性体に相当する分画を四塩化
炭素より再結晶して純粋な〔〕−Z異性体29g
(収率35.9%、n22 D1.5607)および〔〕−E異性体
5.5g(収率6.8%、融点87〜88℃)を得た。展開
溶媒n−ヘキサン/アセトン(10/3)をさらに
通すことによりα−(1,2,4−トリアゾール
−1−イル)ピナコロン10gを回収した。各異性
体の元素分析値および特徴的なNMRスペクトル
の結果を示す。NMRスペクトルは重クロロホル
ムを溶媒として、テトラメチルシランを内部標準
とする化学シフトをδ値で示した。
1−(4−メチルフエニル)−4,4−ジメチル
−2−(1,2,4−トリアゾール−1−イル)−
1−ペンテン−3−オンの
E異性体:
元素分析 C(%) H(%) N(%)
計算値 71.33 7.12 15.60
(C16H19N3O)として
分析値 71.71 7.15 15.20
NMRスペクトル
8.30(1H、シングレツト、トリアゾールプロト
ン)、8.07(1H、シングレツト、トリアゾールプ
ロトン)、7.15(1H、シングレツト、オレフイン
プロトン)
1−(4−メチルフエニル)−4,4−ジメチル
−2−(1,2,4−トリアゾール−1−イル)−
1−ペンテンン−3−オンの
−Z異性体;
元素分析 C(%) H(%) N(%)
分析値 71.50 7.09 17.72
NMRスペクトル
8.13(1H、シングレツト、トリアゾールプロト
ン)、7.95(1H、シングレツト、トリアゾールプ
ロトン)、7.56(1H、シングレツト、オレフイン
プロトン)
実施例 1
1−(4−メチルフエニル)−4,4−ジメチル
−2−(1,2,4−トリアゾール−1−イル)
−1−ペンテン−3−オン(化合物番号5)の
〔〕−E異性体の合成
参考例1で得た1−(4−メチルフエニル)−
4,4−ジメチル−2−(1,2,4−トリアゾ
ール−1−イル)−1−ペンテン−3−オンの
〔〕−Z異性体10.0gをアセトン500mlに溶解し、
500Wの高圧水銀灯を装備した内照式紫外線照射
装置で45℃にて異性化反応を行なつた。反応液の
微量を随時サンプルとして抜き取り、参考例1と
同様の条件でのガスクロマトグラフイーによつて
異性化比〔〕−Z異性体/〔〕−異性体)をモ
ニターしたところ次のような結果を得た。
時間(分) 異性体比(〔〕-Z/〔〕-E)
0 100/ 0
15 15/85
30 7/93
60 6/94
10時間後に反応液を500mlナス型フラスコに移
し減圧下にアセトンを留去して9.8gの結晶を得
た。これを四塩化炭素より再結晶して5.3g(53
%)の結晶を得た。融点87−88℃、この化合物の
アセトン溶液を上記条件のガスクロマトグラフイ
ーを行なつたところ〔〕−Z異性体に相当する
ピークは全く認められなかつた。
実施例 2
1−(4−メチルフエニル)−4,4−ジメチル
−2−(1,2,4−トリアゾール−1−イル)
−1−ペンテン−3−オンの幾何異性体混合物
から〔〕−E異性体の合成
参考例1の反応で得られた〔〕−E/〔〕−
Z=1/4の異性体反応混合物10gを実施例1と
同様の条件で紫外線照射し、9時間後にガスクロ
マトグラフイーで調べたところ〔〕−E/〔〕
−Z存在比は約16/1であつた。
溶媒を留去後得られた結晶を四塩化炭素から再
結晶して5.2gの〔〕−E異性体を単離した。
以下、同様の方法で〔〕−E異性体を製造し
第1表に掲げた。なお比較のために〔〕−Z異
性体についても併せ記載した。表から明らかなよ
うに〔〕−E異性体のオレフインプロトンは
〔〕−Z異性体に比してより高磁場側に認められ
る。Represents a triazolyl group represented by [Formula]. R 2 represents a tert-butyl group or a phenyl group that is unsubstituted or optionally substituted with an alkyl group, an alkoxy group, a phenyl group, or a halogen atom. ] The azole compound represented by
It was discovered that the compound (No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, March 2012) has excellent properties as a bactericidal agent. The triazole compound represented by the general formula [] is disclosed in the above-mentioned publication (Japanese Unexamined Patent Publication No. 130661/1983).
As shown in, for example, it can be produced according to the following reaction, [In the formula, X, n and R have the same meanings as described above. ] It is usually obtained as a mixture of geometric isomers represented by the following general formulas [ ] and [ ]. [In the formula, X, n and R have the same meanings as described above. ] The present inventors continued research from the above standpoint, and as a result (1) One of the geometric isomers of the alcohol compound obtained by reducing each of the geometric isomer ketone compounds of the general formulas [] and []. It has excellent properties as an agricultural and horticultural fungicide, such as having extremely high fungicidal activity against a wider range of plant pathogens than the other. (2) By irradiating one of the geometric isomers or a mixture of geometric isomers of the triazole compound represented by the general formula [], virtually quantitatively,
The inventors have discovered that it is possible to produce geometric isomers of ketone compounds that serve as intermediates for producing more active alcohol compounds, leading to the completion of the present invention. In other words, the two geometric isomers of the triazole compound represented by the general formula
For example, one of the geometric isomers of a triazole compound represented by the general formula [] (hereinafter []-
The olefin proton of -E isomer) is
In the NMR spectrum in deuterated chloroform, the other geometric isomer (hereinafter referred to as []-z isomer)
Alcohol compounds obtained by reducing the []-E isomer (hereinafter referred to as alcohol-E isomers) appear on the higher magnetic field side than the olefin proton of
is an alcohol compound obtained by reducing the []-Z isomer (hereinafter referred to as alcohol-Z isomer)
The []-E isomer can be said to be an important intermediate for producing agricultural and horticultural fungicides with superior properties. []-E isomer can also be obtained pure from the isomer mixture obtained according to the above reaction formula by fractional crystallization or column chromatography (see Reference Example 1), but the method of the present invention can be manufactured more efficiently. That is, by exposing the []-Z isomer to light, it was possible to convert it virtually quantitatively into the []-E isomer. []-Z and []
It has been found that any mixture of -E isomers can be converted under similar conditions virtually quantitatively to the []-E isomer, and the present invention provides a method for preparing the []-E isomer. It can be said that this method provides an excellent method. A more specific method for producing the compound of the present invention will be described below. []-Z isomer or []-Z and []
- by placing the mixture of E isomers in a light-inert solvent under light irradiation, such as a UV lamp or a xenon lamp, or, in the laboratory, under a fluorescent lamp or sunlight. []-E isomer can be produced by placing Commonly used solvents include alcohols such as methanol, ethanol, and propanol, ethers such as ether, tetrahydrofuran, and dioxane, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and aliphatic solvents such as hexane, cyclohexane, and petroleum ether. Examples include hydrocarbons, aromatic hydrocarbons such as benzene, toluene, and xylene. The reaction temperature can be carried out at a temperature at which a normal photoisomerization reaction is carried out, but in actual production it is preferably carried out within the range of 0°C to 100°C. It is of course possible to carry out the reaction by adding a sensitizer used in ordinary photoreactions, such as phenyl ketones such as acetophenone and propiophenone, but no particular advantage is found. The compound of the present invention itself has strong bactericidal activity against various agriculturally harmful pathogenic bacteria, and can be used as a useful fungicide (see Reference Example 2), as well as having herbicidal and plant growth regulating effects. The possibility of use in this field is also recognized. Next, the present invention will be explained in more detail by giving examples and reference examples. Reference example 1 1-(4-methylphenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)
-Synthesis of 1-penten-3-one (geometric isomer mixture) α-(1,2,4-triazol-1-yl)
50 g of pinacolon, 41 g of anhydrous potassium carbonate, 200 ml of acetic anhydride, and 39.7 g of 4-chlorobenzaldehyde were mixed and heated at 90° C. for 12 hours with stirring. After cooling the reaction solution, the precipitate was removed by filtration. Mother liquor at 60℃
The mixture was added dropwise to 500 ml of warm water to decompose the acetic anhydride, then potassium carbonate was added little by little to make it alkaline, and the resulting oil was extracted with 500 ml of ethyl acetate.
The organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. A drop of the residue was taken and made into an acetone solution, and gas chromatography was performed under the following conditions, and the retention time was 250 seconds.
The peak corresponding to the E isomer was detected at 300 seconds []-
A peak corresponding to the Z isomer was observed. The abundance ratio determined from the area percentage was 1/4. The conditions for gas chromatography are as follows. Equipment: JEOL 20KFID detector Column: 5% XE-60, carrier Chromosolve W,
1m glass column Column temperature: 200℃ Vaporization chamber temperature: 240℃ Carrier gas: Nitrogen gas 1Kg/cm 2 The residue was dissolved in 100ml of benzene, passed through a column containing 1.2Kg of silica gel (100-200 mesh), and then Column chromatography was performed using -hexane/acetone (10/1) as a developing solvent. The fractions corresponding to each obtained isomer were recrystallized from carbon tetrachloride to obtain 29 g of pure []-Z isomer.
(yield 35.9%, n 22 D 1.5607) and []-E isomer
5.5 g (yield 6.8%, melting point 87-88°C) was obtained. By further passing a developing solvent n-hexane/acetone (10/3), 10 g of α-(1,2,4-triazol-1-yl)pinacolon was recovered. Elemental analysis values and characteristic NMR spectra of each isomer are shown. The NMR spectrum uses deuterochloroform as a solvent and the chemical shifts are shown as δ values using tetramethylsilane as an internal standard. 1-(4-methylphenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-
E isomer of 1-penten-3-one: Elemental analysis C(%) H(%) N(%) Calculated value 71.33 7.12 15.60 As (C 16 H 19 N 3 O) Analytical value 71.71 7.15 15.20 NMR spectrum 8.30 ( 1H, singlet, triazole proton), 8.07 (1H, singlet, triazole proton), 7.15 (1H, singlet, olefin proton) 1-(4-methylphenyl)-4,4-dimethyl-2-(1,2,4- triazol-1-yl)-
-Z isomer of 1-penten-3-one; Elemental analysis C (%) H (%) N (%) Analysis value 71.50 7.09 17.72 NMR spectrum 8.13 (1H, singlet, triazole proton), 7.95 (1H, singlet, triazole proton), 7.56 (1H, singlet, olefin proton) Example 1 1-(4-methylphenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)
Synthesis of []-E isomer of -1-penten-3-one (compound number 5) 1-(4-methylphenyl)- obtained in Reference Example 1
10.0 g of the []-Z isomer of 4,4-dimethyl-2-(1,2,4-triazol-1-yl)-1-penten-3-one was dissolved in 500 ml of acetone,
The isomerization reaction was carried out at 45°C using an internally illuminated ultraviolet irradiation device equipped with a 500W high-pressure mercury lamp. A small amount of the reaction solution was taken as a sample at any time, and the isomerization ratio []-Z isomer/[]-isomer) was monitored by gas chromatography under the same conditions as in Reference Example 1.The following results were obtained. I got it. Time (min) Isomer ratio ([]-Z/[]-E) 0 100/ 0 15 15/85 30 7/93 60 6/94 After 10 hours, the reaction solution was transferred to a 500 ml eggplant flask and added with acetone under reduced pressure. was distilled off to obtain 9.8 g of crystals. This was recrystallized from carbon tetrachloride and 5.3g (53
%) of crystals were obtained. When an acetone solution of this compound with a melting point of 87-88 DEG C. was subjected to gas chromatography under the above conditions, no peak corresponding to the []-Z isomer was observed. Example 2 1-(4-methylphenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)
Synthesis of []-E isomer from a mixture of geometric isomers of -1-penten-3-one []-E/[]- obtained in the reaction of Reference Example 1
10 g of the isomer reaction mixture of Z = 1/4 was irradiated with ultraviolet rays under the same conditions as in Example 1, and examined by gas chromatography after 9 hours []-E/[]
-Z abundance ratio was approximately 16/1. After evaporating the solvent, the resulting crystals were recrystallized from carbon tetrachloride to isolate 5.2 g of the []-E isomer. Hereinafter, the []-E isomer was produced in the same manner and listed in Table 1. For comparison, the []-Z isomer is also described. As is clear from the table, the olefin proton of the []-E isomer is observed on the higher magnetic field side compared to the []-Z isomer.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】
参考例 2
茎葉散布によるオオムギうどんこ病防除効果
(幼苗試験)
150ml容のプラスチツク製ポツトに砂壊土をつ
め、オオムギ種子(品種:五畝四石)を10〜15粒
播種した。これを18〜23℃の空調温湿で7日間裁
培し、第1本葉が展開したオオムギ幼苗を得た。
この幼苗に乳剤形態の供試化合物の水希釈液をポ
ツトあたり10mlあて茎葉散布した。薬液風乾後幼
苗にオオムギうどんこ病菌(Erysiphe
graminis)を接種し、これを23℃の定温室に入
れ螢光灯照明下で10日間裁培したのち、第1本葉
の発病状態を観察した。発病度は下記の方法によ
つて算出した。すなわち調査葉の病斑出現度に応
じて第2表に示すごとく指数に分類した。[Table] Reference Example 2 Effect of controlling barley powdery mildew by foliage spraying (seedling test) A 150 ml plastic pot was filled with sand-broken soil, and 10 to 15 barley seeds (variety: Goune Shiseki) were sown. This was cultivated for 7 days in an air-conditioned temperature and humidity range of 18 to 23°C to obtain barley seedlings with the first true leaves developed.
A water diluted solution of the test compound in the form of an emulsion was sprayed onto the seedlings at 10 ml per pot. Barley powdery mildew fungus (Erysiphe) appears on young seedlings after air drying the chemical solution.
graminis) was placed in a constant temperature chamber at 23°C and cultured for 10 days under fluorescent lamp illumination, and then the disease state of the first true leaves was observed. The disease severity was calculated by the following method. That is, they were classified into indices as shown in Table 2 according to the degree of appearance of lesions on the investigated leaves.
【表】
つづいて次式により発病後を算出した。
発病後(%)
=Σ(発病指数)×(葉数)/(調査葉数)×100
つづいて防除価を次式より求めた。
防除価(%)
=100−(化合物処理区の発病度)/(無処理区の
発病度)×100
本試験の結果を第3表に示すが、本成積から明
らかなように、本発明化合物は優れたオオムギう
どんこ病防除効果を示し、その効果はオオムギう
どんこ病防除に用いられる比較対照化合物と同等
あるいは優れたものである。[Table] Next, the time after onset of illness was calculated using the following formula. After disease onset (%) = Σ (infection index) × (number of leaves) / (number of investigated leaves) × 100 Next, the control value was calculated from the following formula. Control value (%) = 100 - (incidence in compound-treated area) / (incidence in non-treated area) x 100 The results of this test are shown in Table 3, and as is clear from this accumulation, the present invention The compound exhibits excellent barley powdery mildew control efficacy, and its efficacy is comparable to or superior to a comparative compound used for barley powdery mildew control.
【表】【table】
【表】【table】
Claims (1)
ハロアルキル基、アルコキシ基、フエノキシ基、
シアノ基またはニトロ基を表わし、nは0〜5の
整数を表わし、Rはアルキル基、シクロプロピル
基、またはアルキルスルフエニル基で置換された
アルキル基を表わす。 但し、Rがターシヤリブチル基を表わし、かつ
Xがハロゲン原子またはフエニル基を表わし、n
が1または2を表わす場合を除く。〕 で示されるトリアゾール系化合物の2つの幾何異
性体のうち、オレフインプロトンが重クロロホル
ム中でのNMRスペクトル上、より高磁場側に現
われる幾何異性体化合物。 2 一般式 〔式中、Xは同一または相異なり、アルキル基、
ハロアルキル基、アルコキシ基、フエノキシ基、
シアノ基またはニトロ基を表わし、nは0〜5の
整数を表わし、Rはアルキル基、シクロプロピル
基、またはアルキルスルフエニル基で置換された
アルキル基を表わす。 但し、Rがターシヤリブチル基を表わし、かつ
Xがハロゲン原子またはフエニル基を表わし、n
が1または2を表わす場合を除く。〕 で示されるトリアゾール系化合物の2つの幾何異
性体のうち、オレフインプロトンが重クロロホル
ム中でのNMRスペクトル上、より低磁場側に現
われる幾何異性体を光照射して異性化させること
を特徴とする上記トリアゾール系化合物のオレフ
インプロトンが重クロロホルム中でのNMRスペ
クトル上、より高磁場側に現われる幾何異性体の
製造法。 3 一般式 〔式中、Xは同一または相異なり、アルキル基、
ハロアルキル基、アルコキシ基、フエノキシ基、
シアノ基またはニトロ基を表わし、nは0〜5の
整数を表わし、Rはアルキル基、シクロプロピル
基、またはアルキルスルフエニル基で置換された
アルキル基を表わす。 但し、Rがターシヤリブチル基を表わし、かつ
Xがハロゲン原子またはフエニル基を表わし、n
が1または2を表わす場合を除く。〕 で示されるトリアゾール系化合物の2つの幾何異
性体混合物を光照射して異性化させることを特徴
とする上記トリアゾール系化合物のオレフインプ
ロトンが重クロロホルム中でのNMRスペクトル
上、より高磁場側に現われる幾何異性体の製造
法。[Claims] 1. General formula [In the formula, X is the same or different, an alkyl group,
haloalkyl group, alkoxy group, phenoxy group,
It represents a cyano group or a nitro group, n represents an integer of 0 to 5, and R represents an alkyl group, a cyclopropyl group, or an alkyl group substituted with an alkylsulfenyl group. However, R represents a tertiary butyl group, X represents a halogen atom or a phenyl group, and n
except when represents 1 or 2. ] Among the two geometric isomers of triazole compounds represented by , a geometric isomer compound in which the olefin proton appears on the higher magnetic field side in the NMR spectrum in deuterated chloroform. 2 General formula [In the formula, X is the same or different, an alkyl group,
haloalkyl group, alkoxy group, phenoxy group,
It represents a cyano group or a nitro group, n represents an integer of 0 to 5, and R represents an alkyl group, a cyclopropyl group, or an alkyl group substituted with an alkylsulfenyl group. However, R represents a tertiary butyl group, X represents a halogen atom or a phenyl group, and n
except when represents 1 or 2. ] Among the two geometric isomers of the triazole compound represented by , the geometric isomer in which the olefin proton appears on the lower magnetic field side in the NMR spectrum in deuterated chloroform is isomerized by light irradiation. A method for producing a geometric isomer in which the olefin proton of the above triazole compound appears on the higher magnetic field side in the NMR spectrum in deuterated chloroform. 3 General formula [In the formula, X is the same or different, an alkyl group,
haloalkyl group, alkoxy group, phenoxy group,
It represents a cyano group or a nitro group, n represents an integer of 0 to 5, and R represents an alkyl group, a cyclopropyl group, or an alkyl group substituted with an alkylsulfenyl group. However, R represents a tertiary butyl group, X represents a halogen atom or a phenyl group, and n
except when represents 1 or 2. ] A mixture of two geometric isomers of the triazole compound represented by isomerized by light irradiation, wherein the olefin proton of the triazole compound appears on the higher magnetic field side in the NMR spectrum in deuterated chloroform. Method for producing geometric isomers.
Priority Applications (23)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP12457179A JPS5646870A (en) | 1979-09-26 | 1979-09-26 | Geometrical isomer of triazole compound and its preparation |
US06/130,108 US4554007A (en) | 1979-03-20 | 1980-03-13 | Geometrical isomer of 1-substituted-1-triazolylstyrenes, and their production and use as fungicide, herbicide and/or plant growth regulant |
IT48189/80A IT1143014B (en) | 1979-03-20 | 1980-03-18 | GEOMETRIC ISOMERS OF 1-SUBSTITUTED-1-TRIAZOLISTYRENE HERBICIDE FUNGICIDE AND REGULATOR OF PLANT GROWTH AND PROCEDURE FOR THEIR PREPARATION |
BR8001617A BR8001617A (en) | 1979-03-20 | 1980-03-18 | GEOMETRIC ISOMER OF 1-SUBSTITUTED-1-TRIAZOLYL STYLENE, AND ITS PRODUCTION AND USE AS FUNGICIDE, HERBICIDE AND / OR PLANT GROWTH REGULATOR |
CA000347897A CA1154449A (en) | 1979-03-20 | 1980-03-18 | Geometrical isomer of 1-substituted-1- triazolylstyrenes, and their production and use as fungicide, herbicide and/or plant growth regulant |
NZ193168A NZ193168A (en) | 1979-03-20 | 1980-03-18 | Certain geometric isomers of 1-phenyl-2-(1,2,4-triazol-1-yl)-3-hydrocarbylpropan-3-ols |
AU56571/80A AU536825B2 (en) | 1979-03-20 | 1980-03-19 | Geometrical isomer of 1-substituted-1-triazolyl-styrenes |
DK118580A DK157811C (en) | 1979-03-20 | 1980-03-19 | GEOMETRIC ISOMERS OF 1-SUBSTITUTED-1-TRIAZOLYL CONTROLS, INTERMEDIATE FOR USE BY THEIR PREPARATION AND FUNGICIDE, HERBICIDE AND / OR PLANT GROWTH REGULATOR CONTAINING THE GEOMETRIC ISOMERS |
GB8009190A GB2046260B (en) | 1979-03-20 | 1980-03-19 | Geometrical isomer of 1-substituted-1-triazolylstyrenes and their production and use as fungicides herbicides and/or plant growth regulations |
DE19803010560 DE3010560A1 (en) | 1979-03-20 | 1980-03-19 | GEOMETRIC ISOMERS OF TRIAZOLE COMPOUNDS AND FUNGICIDES, HERBICIDES AND / OR PLANT GROWTH CONTROLLING AGENTS THEREOF |
HU80652A HU186281B (en) | 1979-03-20 | 1980-03-19 | Fungicide, herbicide and control preparation of plant growing and process for producing 1-subsituted-1-triazoly-styrene derivatives used for same |
AR280359A AR226305A1 (en) | 1979-03-20 | 1980-03-19 | GEOMETRIC ISOMER OF DEL-FENIL-2-TRIAZOL (1,2,4) -PROPEN-3-OL USEFUL AS A HERBICIDE AND REGULATOR OF PLANT GROWTH |
FR8006155A FR2460939B1 (en) | 1979-03-20 | 1980-03-19 | 1-TRIAZOLYLSTYRENE 1-SUBSTITUTED GEOMETRIC ISOMERS, THEIR SYNTHESIS INTERMEDIATES, THEIR PRODUCTION AND THEIR USE IN AGRICULTURE AND HORTICULTURE |
CH217080A CH644851A5 (en) | 1979-03-20 | 1980-03-19 | GEOMETRIC E-ISOMERS OF 1-TRIAZOLYL STYRENE SUBSTITUTED. |
IL59671A IL59671A (en) | 1979-03-20 | 1980-03-19 | Geometrical isomers of 1-substituted-1-triazolylstyrenes and their production and use as herbicides and/or plant growth regulants |
PL1980222822A PL123010B1 (en) | 1979-03-20 | 1980-03-19 | Fungicidal, herbicidal and/or plant growth regulating agent and method of manufacture of novel derivatives of triazole |
YU766/80A YU42969B (en) | 1979-03-20 | 1980-03-19 | Process for producing geometric isomers of 1-substituted-1-triazolyl styroles |
NL8001658A NL192791C (en) | 1979-03-20 | 1980-03-20 | Substantially pure geometric isomer of 1-substituted 1-triazolystyrenes, methods of preparation thereof, as well as use as a fungicide, herbicide and / or plant growth control agent. |
FR8015965A FR2457858A1 (en) | 1979-04-05 | 1980-07-18 | Geometrical isomers of 1-phenyl-2-triazolyl-penten-3-ol - and ether(s), useful as fungicides, herbicides, growth regulators and antimycotics |
FR8015966A FR2457859A1 (en) | 1979-04-05 | 1980-07-18 | GEOMETRIC ISOMERS OF 1-SUBSTITUTED 1-TRIAZOLYLSTYRENES, THEIR PREPARATION AND THEIR USE AS FUNGICIDES |
US06/772,429 US4749716A (en) | 1979-03-20 | 1985-09-04 | Geometrical isomer of 1-substituted-1-triazolystyrenes |
MY898/87A MY8700898A (en) | 1979-03-20 | 1987-12-30 | Geometrical isomer of 1-substituted-1-triazolystyrenes, and their production and use as fungicides herbicides and/or plant growth regulants |
LVP-92-391A LV10023B (en) | 1979-03-20 | 1992-12-22 | Geometrical isomer of 1-substituted-1-triazolylstyrenes, and their production and use as fungicide, herbicide and/or plant growth regulant |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP12457179A JPS5646870A (en) | 1979-09-26 | 1979-09-26 | Geometrical isomer of triazole compound and its preparation |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5646870A JPS5646870A (en) | 1981-04-28 |
JPH0211589B2 true JPH0211589B2 (en) | 1990-03-14 |
Family
ID=14888771
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP12457179A Granted JPS5646870A (en) | 1979-03-20 | 1979-09-26 | Geometrical isomer of triazole compound and its preparation |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5646870A (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63125276A (en) * | 1986-11-14 | 1988-05-28 | 京楽産業株式会社 | Winning apparatus of pinball machine |
JPH0615605Y2 (en) * | 1988-03-04 | 1994-04-27 | 豊丸産業株式会社 | Prize winning device for pachinko machines |
JPH0615604Y2 (en) * | 1988-03-05 | 1994-04-27 | 豊丸産業株式会社 | Prize ball selection device for pachinko machines |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS55147265A (en) * | 1979-04-05 | 1980-11-17 | Sumitomo Chem Co Ltd | Triazole geometrical isomer compound and its preparation |
JPS55154961A (en) * | 1979-05-19 | 1980-12-02 | Bayer Ag | Geometrical isomer of 4*44dimethyll11phenyll *1*2*44triazolee11yl**11pentenee33ol |
-
1979
- 1979-09-26 JP JP12457179A patent/JPS5646870A/en active Granted
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS55147265A (en) * | 1979-04-05 | 1980-11-17 | Sumitomo Chem Co Ltd | Triazole geometrical isomer compound and its preparation |
JPS55154961A (en) * | 1979-05-19 | 1980-12-02 | Bayer Ag | Geometrical isomer of 4*44dimethyll11phenyll *1*2*44triazolee11yl**11pentenee33ol |
Also Published As
Publication number | Publication date |
---|---|
JPS5646870A (en) | 1981-04-28 |
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